ZTbe  Wniversits  ot  dbicaao 


I.  Colors  of  the  Second  Order 
II.  Mercuri-Organic  Derivatives 


A  DISSERTATION 

SUBMITTED  TO  THE  FACULTY 

OF  THE  OGDEN  GRADUATE  SCHOOL  OF  SCIENCE 

IN  CANDIDACY  FOR  THE  DEGREE  OF 

DOCTOR  OF  PHILOSOPHY 


DEPARTMENT   OF   CHEMISTRY 


BV 

MORRIS  SEUG  KHARASCH 


Private  Edition,  Distributed  By 

THE  UNIVERSITY  OF  CHICAGO  LIBRARIES 

CHICAGO,  ILLINOIS 

1921 


ZTbe  '(University  .of  Chicago 


I.  Colors  of  the  Second  Order 
II.  Mercuri-Organic  Derivatives 


A  DISSERTATION 

SUBMITTED  TO  THE  FACULTY 

OF  THE  OGDEN  GRADUATE  SCHOOL  OF  SCIENCE 

IN  CANDIDACY  FOR  THE  DEGREE  OF 

DOCTOR  OF  PHILOSOPHY 


DEPARTMENT   OF    CHEMISTRY 


BY 

MORRIS  SELIG  KHARASCH 


Private  Edition,  Distributed  By 

THE  UNIVERSITY  OF  CHICAGO  LIBRARIES 

CHICAGO,  ILLINOIS 

1921 


- 


NITROSO-TRIPHENYLAMINE  AND    COLORS  OF  THE  SECOND 

ORDER1 

It  is  a  well-known  rule2  that  the  color  of  a  yellow  dye  changes  with  in- 
crease of  molecular  weight  to  orange,  red,  violet,  blue,  and  finally  to  green. 
Each  one  of  these  colors  is  called  lower  than  the  preceding  one,  and  higher 
than  the  following  one.  Generally,  we  can  lower  the  color  by  the  intro- 
duction of  alkyl  or  aryl  radicles  into  the  auxochromic  or  chromophoric 
groups  of  the  dye. 

The  spectroscopic  explanation  of  this  behavior  of  dyes  is  that  a  yellow 
dye  has  an  absorption  band  in  the  violet,  and  any  increase  in  the  molec- 
ular weight  decreases  the  number  of  vibrations  corresponding  to  this  ab- 
sorption band  causing  the  band  to  shift  toward  the  red  end  of  the  spectrum. 
When  the  absorption  band  is  in  the  blue  the  compound  appears  orange, 
and 'as  the  absorption  band  goes  through  green,  yellow,  orange  to  red,  the 
color  of  the  respective  compounds  successively  changes  to  red,  violet,  blue, 
and  green.  A  compound  has  the  color  complementary  to  that  of  its  maxi- 
mum absorption.  On  the  other  hand,  if  in  the  molecule  of  a  yellow  dye 
we  make  such  changes  as  generally  tend  to  produce  a  higher  color,  then  the 
absorption  bands  shift  into  the  ultra-violet  part  of  the  spectrum,  the  com- 
pound becoming  colorless. 

Absorption  colors  have  very  much  in  common  with  interference  colors. 
The  colors  of  Newton,  for  instance,  are  also  produced  by  an  absorption 
band  going  through  the  spectrum  in  the  same  direction  in  which  the  ab- 
sorption bands  of  chemical  compounds  shift  with  increase  of  molecular 
weight.  Thin  layers  of  any  oil,  soap  bubbles  and  glass  are  first  yellow 
in  reflected  light,  and  as  the  thickness  of  the  layer  increases,  the  color  be- 
comes orange,  red,  violet,  blue  and  green.  The  last  color  has  an  absorp- 
tion band  in  the  red,  but  in  the  violet  end  of  the  spectrum  there  appears 
a  new  band.  If  the  layer  becomes  still  thicker,  the  first  band  (in  the  red) 
shifts  into  the  ultra-red,  and  we  have  only  the  second  band,  which  is  in 
the  violet.  Our  layer  is  now  again  yellow  but  yellow  of  the  second  order. 

1  This  work  was  carried  out  in  co-operation  with  Professor  J.  F.  Piccard  and 
published  in  /.  Am.  Chem.  Soc.,  40,  1074  (1918),  in  an  article  by  J.  F.  Piccard  and  M. 
S.  Kharasch. 

-  Xk't/ki,  TV/7/,  des  Vereins  zur  Forderung  des  Geiuerbefleisses,  58,  231  (1879). 


458685 


Some  years  ago  Professor  Piccard  became  interested  in  what  would 
happen  if  a  dye  with  a  lower  color  than  green  were  prepared.  This  prob- 
lem was  undertaken  by  me  in  collaboration  with  Professor  Piccard.  The 
number  of  green  dyes  is  relatively  small,  and  most  of  them  have  already  so 
many  alkyl  and  aryl  radicles  in  their  auxochrome  and  chromophore  groups 
that  any  further  increase  in  molecular  weight  is  almost  impossible.  In  the 
field  of  meriquinoid  dyes  an  opportunity  for  such  experiments  was  found. 
These  dyes  begin  with  yellow  (meriquinone  di-immonium  salts) 

C1NH,  =  C6H4  =  NHoCl 

NH2  —  C6H4  —  NH2 

and  go  to  green  (meri-tetramethyl-diphenoquinone-di-immonium  salt). 
When  we  substituted  8  phenyl  groups  for  the  8  methyls  in  the  last  named 
green  compound,  a  substitution  which  always  lowers  the  color,  a  new 
yellow  dye  was  obtained  which  was  the  first  representative  of  absorption 
colors  of  second  order,  namely, 

CH3COO.(C6H5)2N  =  C6H4  =  C6H4  =  N(C6H5)2.OOCCHJ 

(CeH6)2N  —  C6H5  —  C6H4  —  N(C6H5)2 
meri-tetraphenyl-diphenoquinone-di-immonium    acetate. 

The  above  mentioned  experiments  demonstrate  that  the  rule  for  inter- 
ference colors  of  second  order  holds  good  in  case  of  absorption  colors. 
The  first  absorption  band,  or  group  of  absorption  bands,  is  always  followed 
by  a  second  one  which  corresponds  approximately  to  double  the  number 
of  vibrations  of  the  first  one ;  it  is  the  octave  of  the  first. 

Since  the  paper  of  Piccard1  was  published,  attention  has  been  called  to  a 
few  more  examples  of  colors  of  the  second  order,  but  none  of  them  gives  a 
much  lower  color  than  yellowish  green,  or  greenish  yellow.  The  new 
theory  led,  however,  to  such  encouraging  results,  in  explaining  the  colors 
of  new  compounds,  that  we  have  tried  to  go  one  step  further  to  prepare 
an  orange  compound  of  the  second  order.  We  have  chosen  the  group  of 
p-nitrosoanilines  for  this  work. 

In  the  ^-nitrosoanilines  the  dimethyl  compound  is  already  yellowish 
green.  The  monophenyl  (/?-nitroso-diphenylamine)  is  greenish  yellow  in 
benzene  solution,  while  in  alcohol  it  is  orange.2 

CH3NCH3  HNC6H5 


Green.  Greenish  yellow. 


NO  NO 

1  Jean  Piccard,  Ber.,  46,  1843  (1913). 

2  There  is  very  little  doubt  as  to  the  fact  that  the  alcoholic  solution  of  the  />-nitroso- 
diphenylamine  contains  an  addition  compound.     See  F.  Strauss  and  Zeime,  Ber.,  46, 
2267  (1913)- 


To  complete  the  above  given  group  of  dyes,  and  to  compare  their  colors, 
it  was  necessary  to  have  the  diphenyl-nitrosoaniline  (nitroso-triphenyl- 
amine).  We  were  puzzled  by  the  fact  that  nitroso-triphenylamine,  which 
is  very  interesting  from  a  purely  chemical  point  of  view,  had  not  as  yet 
been  prepared,  and  it  was  not  without  apprehension  that  we  began  this 
work.  In  the  literature  we  found  mention  of  several  vain  attempts  to 
prepare  this  compound.  It  seemed,  from  all  the  work  done,  as  if  in  tri- 
phenylamine  the  nitrogen  had  lost  all  influence  on  the  rest  of  the  mole- 
cule, the  ^-hydrogen  atoms  behaving  like  the  hydrogen  in  benzene.  The 
nitro  compound  is  easily  formed,  but  nitrous  acid  does  not  give  a  nitroso 
derivative.  If  any  action  took  place  at  all,  the  only  isolated  product  of 
the  reaction  was  the  ^-nitro-triphenylamine.  On  the  other  hand,  we 
know  from  the  work  of  Wieland  that  triphenylamine  gives  on  oxidation 
derivatives  of  tetraphenylbenzidine. 

After  experimenting  for  some  time  and  obtaining  only  the  previously 
mentioned  derivatives,  we  finally  succeeded  in  working  out  a  method  for 
the  preparation  of  nitroso-triphenylamine.  While  working  out  this  method, 
we  were  influenced  by  the  following  considerations.  In  the  well-known 
Fisher-Hepp  reaction,  the  parahydrogen  changes  place  with  the  — NO 
of  the  nitrosamine  group. 

C6H5  —  N  —  CGH4  —  H  C6H5  —  N  —  C6H4  —  NO 

I  ~*  I 

NO  H 

We  thought  that  it  might  not  be  essential  that  the  — NO  group  should  be 
in  the  same  molecule  as  the  hydrogen,  so  we   tried  to  duplicate  the  con- 
ditions of  the  Fisher-Hepp  reaction  as  well  as  we  could,  except  that  the 
—NO  group  was  attached  to  another  molecule,  by  using  amyl  nitrite. 
(C6H5)2N  —  C6H4  —  H  +  C5HnO  —  NO  — > 

(C6H5)2N  —  C6H4  —  NO  +  CsHnO  —  H. 

Experimentally  this  was  carried  out  by  treating  a  suspension  of  triphenyl- 
amine in  absolute  alcohol,  saturated  with  hydrogen  chloride,  with  amyl- 
nitrite  at  — 5°.  In  this  way  we  obtained  the  .nitroso  compound,  the  yield 
being  nearly  quantitative  with  respect  both  to  the  triphenylamine  and  the 
amylnitrite. 

The  new  compound  was  to  our  surprise  a  chloride  which  could  easily 
be  recrystallized  from  methyl  alcohol.  The  chloride  is  without  doubt 
C1(C6H5)2N  :  C6H4  :  NOH  (diphenyl-quinone-monimine-oxime  chloride)1 
triphenylamine  having  no  affinity  for  HC1. 

Nitroso-triphenylamine  was  easily  prepared  by  the  hydrolysis  of  this 
salt  with  water. 

The  color  of  the  base  and  the  chloride  are  alike,  but  we  must  not  forget 
1  We  shall  use  the  abbreviation  nitroso-triphenylamine  hydrochloride  hereafter 
in  referring  to  this  compound. 


6 

that  the  former  is  orange  of  the  second  order,  and  the  latter  orange  of  the 
first  order.  The  colors  of  the  chlorides  of  nitroso-anilines  begin  with  light 
yellow,  and  are  very  slightly  lowered  by  the  introduction  of  methyl  groups. 
Even  the  monophenyl  derivative  is  only  orange-yellow,  so  we  could  not 
expect  a  much  lower  color  than  orange -yellow  for  a  diphenyl  derivative. 

On  the  other  hand  the  color  of  the  free  bases  begins  with  green  and  goes 
to  greenish  yellow  (nitroso-diphenylamine).  For  the  next  member  we 
must  expect  a  still  lower  color. 

The  nitroso  group  of  the  nitroso-triphenylamine  is  in  the  para  position. 
This  was  proved  by  reducing  the  nitroso-triphenylamine  with  zinc  and 
acetic  acid  to  the  amino  compound.  This  in  turn  was  converted  with 
acetyl  chloride  into  the  acetyl  derivative,  which  was  found  to  be  identical 
with  that  prepared  by  Herz  from  p-nitro  triphenylamine.1 

Experimental  Part. 

The  Preparation  of  Triphenylamine. — The  following  modified  method 
of  Irma  Goldberg  and  Marie  Nimerovsky2  for  preparing  triphenylamine 
gave  very  satisfactory  results:  A  mixture  of  116  g.  of  diphenylamine, 
140  g.  of  phenyliodide,  72  g.  of  potassium  carbonate  (1.5  times  the  theo- 
retical quantity),  2.5  g.  of  catalytic  copper3  and  300  cc.  of  nitrobenzene 
was  heated  for  12  hours  at  207  °4  in  a  copper  flask,  fitted  with  an  air  con- 
denser. The  brown-colored  solution  was  then  subjected  to  steam  distilla- 
tion, whereby  the  nitrobenzene  and  the  excess  of  phenyliodide  were  sepa- 
rated from  the  products  of  the  reaction.  Benzene  was  added  to  the  mix- 
ture of  di-  and  triphenylamines,  .potassium  iodide  and  copper  and  the  whole 
filtered  through  glass  wool,  to  free  it  from  copper.  The  benzene  solution 
was  then  separated  from  the  water,  dried  with  anhydrous  sodium  sulfate, 
and  the  benzene  distilled  off.  The  crude  product  (157  g.)  was  dissolved  in 
hot  glacial  acetic  acid.  Upon  cooling,  the  triphenylamine  crystallized 
out  (120  g.,  m.  p.  124.5°).  When  recrystallized  from  methyl  alcohol  the 
triphenylamine  was  obtained  in  small,  almost  colorless  crystals,  melting 
at  127°. 

Nitroso-triphenylamine  Hydrochloride. — Twenty  g.  of  triphenylamine 
was  dissolved  in  170  cc.  of  hot  absolute  alcohol,  the  solution  cooled  rapidly 
and  the  resulting  suspension  treated  with  300  cc.  of  a  solution  of  alcohol 
saturated  with  hydrogen  chloride.  Dry  hydrogen  chloride  was  then  passed 
through  the  suspension,  and  amyl  nitrite  slowly  added,  the  whole  being 
well  cooled  ( — 5°)  and  constantly  shaken  during  the  operation.  The  solu- 
tion first  turned  blue,  and,  as  more  amyl  nitrite  was  added,  red.  The  end 
of  the  reaction  was  ascertained  by  diluting  a  drop  of  the  solution  with 

1  /.  Am.  Chem.  Soc.,  39,  2006  (1917);  also  Ber.,  40,  2451  (1907). 

2  Ber.,  40,  2451   (1907). 

3  /.  Am.  Chem.  Soc.,  39,  2006  (1917). 

4  The  temperature  is  that  of  the  oil  bath  in  which  the  copper  flask  was  immersed. 


water  and  testing  with  potassium  iodide-starch  paper.  The  solution  was 
allowed  to  stand  for  2  hours  longer  at  — 20°,  while  a  slow  stream  of  dry 
hydrogen  chloride  was  passed  through  it.  An  orange-red  to  carmine 
product  separated  out,  the  color  depending  on  the  quantity  of  hydrogen 
chloride  introduced.  This,  the  hydrochloride  of  nitroso-triphenylamine, 
was  filtered  off  and  washed  with  absolute  alcohol.  The  yield  is  very 
good  (20  g.). 

It  is  important  to  note  that  sometimes  smaller  or  greater  quantities  of 
the  nitrotriphenylamine  are  formed  along  with  the  nitroso  compound, 
this  depending  entirely  on  the  quality  of  the  amyl  nitrite  used.  For  puri- 
fication the  nitrosotriphenylamine  hydrochloride  thus  obtained  was  first 
converted  into  the  free  base,  by  suspending  the  hydrochloride  in  cold 
water  for  2  hours.  It  was  then  filtered,  washed  with  cold  water  until  a 
sample  of  the  washings  gave  no  precipitate  with  silver  nitrate,  and  dried 
in  a  vacuum  desiccator.  When  absolutely  dry,  the  free  base  was  dissolved 
in  ether  (dried  over  calcium  chloride)  and  its  hydrochloride  precipitated 
by  dry  hydrogen  chloride.  The  nitrotriphenylamine  remained  in  solu- 
tion. The  hydrochloride  when  recrystallized1  from  ethyl  alcohol  (i  g.  in 
30  cc.)  Was  obtained  in  long,  brown  needles  melting  at  178°. 

The  chlorine  was  determined  by  addition  of  AgNOs  to  the  water  extract  of  the 
hydrochloride. 

Subst,,  0.5000;  AgCl,  0.2283. 

Calc.  for  CisH15N2OCl:  Cl,  n  .42.     Found:  u  .30. 

p-Nitroso-triphenylamine.— The  free  base,  obtained  by  hydrolysis  of 
the  pure  hydrochloride,  was  recrystallized  twice  from  methyl  alcohol,  giv- 
ing beautiful,  long,  brown  needles,  melting  at  120.5°  (corr.).  The  pow- 
dered substance  is  orange. 

Subst.,  o .  1268,  o .  1012 ;  CC>2,  o  .3660,  o  .2923 ;  H2O,  o  .0602,  o  .0473,  o  .2295,  o .  1327 ; 
21  .20,  12  .40  cc.  dry  N2  at  20°,  24°  and  735  .5,  735  .5  mm. 

Calc.  for  CisHnNoO:  C,  78.83;  H,  5.15;  N,  10.27.     Found:  C,  78.70,  78.76;  H, 
5  .27,  5  .i9;N,  10.42,  10.40. 

The  nitroso-triphenylamine  is  soluble  in  methyl  alcohol  (i  g.  per  30  cc. 
of  the  boiling  alcohol),  more  so  in  ethyl  alcohol,  and  very  easily  in  ether 
and  benzene.  In  an  excess  of  dil.  sulfuric  or  hydrochloric  acid  the  nitroso- 
triphenylamine  dissolves  with  a  red  color,  and  is  not  precipitated  by  the 
addition  of  water.  An  acetic  acid  solution  of  the  base  has  the  color  of 
bromine. 

Summary. 

1.  It   is   possible — under   certain   conditions — to   introduce    a   nitroso 
group  into  the  molecule  of  triphenylamine. 

2.  The  nitroso-triphenylamine  so  formed  is  a  para  compound. 

3.  The  color  of  /?-nitroso-triphenylamine  is  orange  of  the  second  order. 

1  The  yield  was  better  if  after  cooling  it  at  — 20°  we  introduced  dry  HC1  gas  into  the 
solution. 


The  following  table  shows  the  colors  of  the  different  £>-nitroso-anilines : 

Color. 


Formula. 


In  ben- 

In alco- 

In alcohol 

Salt. 

Base. 

zene  sol. 

hol  sol. 

water  sol. 

yellow 

blue-green 

blue-green 

blue-green 

(melted) 

yellow 

yellowish 

2 

green 

yellow 

yellowish 

yellowish 

greenish 

yellow 

green 

green 

yellow 

orange- 

orange 

greenish 

yellowish 

orange 

brown 

yellow 

orange 

orange- 

orange 

yellow 

orange 

orange- 

brown 

red 

H2N.C6H4.NO  ...... 

(CH.,)2N.C6H4.NO.. 
(C6H5)HNC6H4:NO 


1  We  indicate  here  the  color  of  nitroso-benzene,  although,  strictly  speaking,  it  does 
not  belong  to  the  same  family. 

2  We  do  not  know  why  this  mother-substance  is  much  less  soluble  than  the  other 
members  of  the  group.     It  is  probably  in  connection  with  this  phenomenon  that  the 
solutions  of  , this  compound  are  more  yellowish  than  those  of  the  dimethyl  derivatives. 


II 

AROMATIC  MERCURI-ORGANIC  DERIVATIVES.1 

During  the  course  of  investigation  of  mercuri-organic  derivatives  under- 
taken for  the  Sprague  Memorial  Institute,  the  amount  of  data  has  ac- 
cumulated to  such  an  extent  that  it  has  been  deemed  advisable  to  publish 
some  of  the  results  thus  far  obtained.  This  paper  contains  some  pre- 
liminary work  on  the  preparation  of  a  6-membered  atomic  heterocyclic 
compound  which  contains  a  metal  in  place  of  a  non-metal.  In  this  case 
mercury  was  the  metal  experimented  with.  It  was  put  in  place  of  nitro- 
gen in  a  ring  of  the  azine  type.  Work  is  now  being  carried  on  to  substi- 
tute mercury  for  oxygen,  sulfur,  and  nitrogen,  in  the  type  of  rings  illus- 
trated below. 

Rx        /Cl  H 


H 

A  detailed  study  of  the  influence  of  different  groups  on  the  position 
taken  by  mercury  when  introduced  into  a  substituted  benzene  nucleus 
is  also  under  investigation. 

The  theory  of  mercurization  will  be  published  at  a  later  date. 

Experimental. 

The  Preparation  of  w-Bromo-dimethyl-anilme,  m-BrCeH^NXCHs)*. — 
This  compound  \vas  first  prepared  by  Wurster,2  by  treating  w-bromo-aniline 
with  methyl  iodide  in  a  sealed  tube.  The  method  has  the  disadvantage 
that  large  quantities  of  w-bromo-dimethyl-aniline  cannot  be  made  in  a 
single  operation.  Since  we  were  not  interested  in  obtaining  pure  ?n-bromo- 
dimethyl-aniline  as  such,  but  a  pure  £-nitroso-w-bromo-dimethyl-aniline, 
the  following  method  was  adopted.  A  quantity  of  w-bromo-aniline 
(?5  g-)  was  suspended  in  water  (900  cc.)  and  heated  to  about  80°.  Sodium 
carbonate  (300  g.)  and  dimethyl  sulfate  (300  g.)  were  then  added  in 
small  portions,  care  being  taken  that  the  solution  was  always  alkaline. 
The  addition  should  take  about  i .  5  hours.  After  all  of  the  dimethyl 
sulfate  had  been  added,  the  solution  was  agitated  for  an  hour  and  then 
subjected  to  steam  distillation.  The  oil  which  came  over  was  separated 

1  The  material  presented  here  was  published  in  the  /.  Am.  Chem.  Soc.,  42,  1855 
(1920)  in  an  article  by  M.  Kharasch  and  J.  F.  Piccard. 

2  Wurster,  Ber.,  12,  1818  (1879). 


10 

from  the  distillate,  the  latter  extracted  twice  with  ether,  and  the  portions 
combined.  The  ether  solution  was  dried  with  sodium  sulfate,  the  ether 
distilled  off,  and  the  oil  distilled  in  vacua.  A  colorless  oil  came  over  which, 
however,  turned  yellow  on  standing.  Yield,  75  g. 

The  product  thus  obtained  contains  unchanged  m-bromo-aniline, 
w-bromo-monomethyl-aniline  and  w-bromo-dimethyl-aniline.  To  sepa- 
rate these  3  substances,  the  usual  method  was  employed.  The  oil  was 
dissolved  in  2.5  mols.  of  20%  hydrochloric  acid,  the  solution  cooled  to 
o°,  and  the  calculated  amount  of  sodium  nitrite1  dissolved  in  a  little  water 
was  added  in  small  amounts.  The  hydrochloride  of  the  p-nitroso-m- 
bromo-dimethyl-aniline  separated.  The  solution  was  then  extracted 
repeatedly  with  ether  until  a  sample  test  showed  the  absence  of  w-bromo- 
pbenyl  methyl  nitrosamine  in  the  latter.2  The  precipitate — the  hydro- 
cnloride  of  the  ^-nitroso-w-bromo-dimethyl-aniline — was  then  filtered 
off  and  dried  in  a  vacuum  desiccator. 

^-Nitroso-  w-bromo-dimethyl-aniline,  (CHs^NCeHsBrNO. — This  com- 
pound was  alsc  prepared  by  Wurster,  who  gave  its  melting-point  but  no 
analytical  data,  owing  to  the  fact  that  the  compound  decomposed  when 
he  tried  to  bring  it  to  constant  weight  by  drying  it  on  the  water-bath. 
The  compound  is  also  not  recorded  in  Richter's  Lexikon.  It  was  thought, 
therefore,  advisable  to  analyze  it. 

A  quantity  of  the  hydrochloride  of  £-nitroso-w-bromo-dimethyl -aniline 
(5  g-)  was  suspended  in  75  cc.  of  water,  cooled  to  o°,  40  cc.  of  ether  added, 
and  enough  carbonate  to  render  the  solution  decidedly  alkaline.  The 
ether  extract  was  then  separated  from  the  solution,  and  the  latter  ex- 
tracted 3  more  times  with  ether,  50  cc.  being  used  each  time.  The  ether 
extracts  were  combined,  dried  with  sodium  sulfate,  and  3/4  of  the  ether 
distilled  off.  The  solution  was  then  transferred  to  an  evaporating  dish 
and  allowed  to  evaporate  spontaneously.  Beautiful  long  green  needles 
were  obtained  which  melted  with  decomposition  at  i48°.3  For  analysis 
the  base  was  recrystallized  twice  from  very  small  amounts  of  ether. 
Subs.,  0.1082:  AgBr,  0.0886. 
Calc.  for  C8HnON2Br:  Br,  34.87.  Found:  34.84. 

m  -  Bromo  -  dimethyl  -  p  -  phenylene  -  diamine  Dihydrochloride> 
BrNHoC6H3N(CH.02.2HCl.— The  hydrochloride  of  £-nitroso-m-bromo-di- 
methyl-aniline  was  reduced  in  the  following  manner.  Twice  the  cal- 
culated amount  of  stannous  chloride  necessary  for  the  reduction  was  dis- 
solved in  cone,  hydrochloric  acid,  the  solution  diluted  somewhat,  warmed 
to  40°,  and  the  £-nitrOso-w-bromo-dimethyl-aniline  hydrochloride,  mixed 

1  To  avoid  an  excess  of  sodium  nitrite,  the  oil  was  assumed  to  be  pure  w-bromo- 
dimethyl-aniline. 

2  Lieberman's  nitrosamine  test. 

1  Wurster  also  gave  148°  as  the  melting-point  of  the  compound. 


11 

with  hydrochloric  acid  to  the  consistency  of  a  thick  paste,  added  to  it 
in  small  portions.  The  reduction  was  practically  instantaneous.  The 
complex  tin  salt  of  the  dihydrochloride  of  the  w-bromo-dimethyl-£>- 
phenylene-diamine  separated.  Enough  water  was  then  added  to  bring 
it  back  into  solution,  and  the  tin  precipitated  as  stannic  sulfide  from  the 
hot  solution  with  hydrogen  sulfide.  Before  being  filtered  the  solution 
was  diluted  with  an  equal  amount  of  water,  warmed  to  80°,  and  hydrogen 
sulfide  passed  through  it  for  a  half  an  hour  longer.  This  procedure  has 
been  found  very  satisfactory,  requiring  very  little  time  and  precipitating 
the  tin  quantitatively  in  one  operation.  The  water  in  the  filtrate  was 
distilled  off  in  vacua.  The  dihydrochloride  of  w-bromo-dimethyl-£- 
phenylene-diamine  remained  behind.  It  was  purified  by  preparation 
of  the  free  base  and  distillation  of  the  latter  in  vacua.  The  base  was  then 
dissolved  in  ether  and  dry  hydrogen*  chloride  passed  into  the  solution. 
The  dihydrochloride  was  precipitated.  It  was  dried  in  a  vacuum  desic- 
cator. 

Subs.,  0.1941 :  16.80  cc.  dry  N2  at  20°  and  726.3  mm. 
-  Calc.  for  CsHi0N2Br.2HCl:  N,  9.81.     Found:  9.64. 

m-Bromo-dimethyl-^-phenylene-diamine,  BrNH2C6H3N(CH3)2. — The 
free  base  was  obtained  by  the  method  previously  outlined.  The  oily 
distillate  solidified  on  cooling  in  white,  almost  colorless,  needles;  m.  p. 
47.5°.  The  free  base  turned  dark  on  exposure  to  light  and  air.  When 
it  was  dissolved  in  dil.  hydrochloric  acid  and  the  solution  was  saturated 
with  hydrogen  sulfide  and  treated  with  ferric  chloride,  an  intensely  blue 
coloration  was  produced. 

Subs.,  0.2749:  AgBr,  0.2406. 

Calc.  for  C8HnN2Br:  Br,  37.18.     Found:  37.25. 

o-Dibromo-Bindschedler's  Green. — The  same  method  was  employed 
as  was  used  originally  by  Bindschedler  for  the  preparation  of  Bindsched- 
ler's  Green.1  To  a  mixture  of  2. 15  g.  of  w-bromo-dimethyl-£-phenylene- 
diamine  and  2  g.  of  w-bromo-dimethyl-aniline,2  2  g.  of  cone,  hydrochloric 
acid  in  50  cc.  of  water  was  added.  The  solution  was  cooled  to  — 2° 
and  oxidized  by  a  solution  of  2  g.  of  potassium  dichromate  and  0.6  g. 
of  glacial  acetic  acid  in  20  cc.  of  water.  The  oxidizing  agent  was  added 
drop  by  drop.  The  flask  was  shaken  continuously  during  the  addition 
of  the  oxidizing  agent.  The  dyestuff  partly  precipitated  out.  Sufficient 
water  was  then  added  to  redissolve  it,  the  solution  heated  to  40-50°  and 
5  g.  of  zinc  chloride  added  to  it.  It  was  allowed  to  stand  in  ice-water 
for  2  hours  longer  and  the  precipitate  collected  on  a  filter,  washed  with 
a  small  quantity  of  cold  water,  then  with  alcohol,  and  finally  with  ether. 
It  was  dried  in  a  vacuum  desiccator.  A  dark  amorphous  powder  was 

1  Bindschedler,  Ber.,  16,  864  (1883). 

2  Prepared  by  the  method  of  Wurster,  ibid.,  16,  864  (1883). 


12 

thus  obtained  which  was  slightly  soluble  in  water,  imparting  to  the  latter 
an  intensely  green  color.     The  yield  was  very  good. 

Subs.,  0.3618:  27.40  cc.  dry  N2  at  24.5°  and  731  mm. 

Subs.,  0.4860:  ZnO,  0.0382. 

Calc.  for  C32H36N6Br4Cl2.ZnCl2:  N,  8.25;  Zn,  6.37.     Found:  N,  8.36;  Zn,  6.31. 
The  analysis  readily  shows  that  in  this  case  also  2  molecules  of  the  dye 
combine  with  one  of  zinc  chloride. 

The  mercuric  chloride  double  salt  was  obtained  by  solution  of  the  zinc 
chloride  double  salt  in  water  at  40-50°,  and  addition  of  mercuric  chloride. 
The  structure  of  the  compound  thus  obtained  is  expressed  by  the  follow- 
ing formula, 

VN~VNi        \ 

}  I         I  ]  .  HgCl2. 

/\Br'  Br//\//\N(CH3)2/2 
1 

Subs.,  0.1373:  HgS,  0.0278. 
Calc.  for  C32H36Br4Cl2.HgCl2:  Hg,  17.17.     Found:  17.47. 

Work  is  also  under  way  on  the  isolation  of  the  leuco-dibromo-Bind- 
schedler's  Green,  and  the  replacing  in  the  latter  of  the  2  bromine  atoms 
by  mercury  to  give  a  compound  of  the  following  type, 


\N(CH3)2 

which,  when  oxidized,  would  give  a  representative  of  a  new  class  of  or- 
ganic mercury  derivatives. 

m  -  Bromo  -  phenylmethyl  -  nitrosamine,  m-BrC6H4N(CH3NO).  —  As 
previously  stated,  the  methylation  of  w-bromo-aniline  by  the  use  of  di- 
methyl sulfate  gave  rise  to  2  derivatives,  the  mono-methyl  and  the  di- 
methyl w-bromo-anilines.  These  2  were  separated  by  the  use  of  sodium 
nitrite  as  given  in  detail  in  the  preparation  of  £-nitroso-w-bromo-dimethyl- 
aniline.  The  ether  extract  of  the  acid  solution  contained  the  m-bromo- 
methylphenyl-nitrosamine.  The  ether  was  distilled  off  and  the  oil  sub- 
jected to  steam  distillation.  The  distillate  was  then  extracted  with 
ether,  the  solution  dried  with  sodium  sulfate,  and  the  ether  distilled  off. 
When  the  sides  of  the  crystallizing  dish  were  cooled  and  scratched  the  oil 
solidified  in  feathery  clusters  of  fine  yellowish  needles;  m.  p.,  49°.  Yield, 
log. 

Subs.,  0.2049:  AgBr,  0.1782. 

Calc.  for  C7H7ON2Br:  Br,  37.17.     Found:  Br,  37.01. 

The  compound  gives  the  characteristic  Lieberman's  nitroso-amine  re- 
action and  in  the  pure  condition  is  very  stable. 


13 

£-Nitroso-w-bromo-monomethylaniline,  BrNOC6H3NHCH3.  —  The 
ra-bromo-methylphenyl-nitrosamine  was  rearranged  according  to  the 
method  of  Fisher  and  Hepp.1  The  nitrosamine  (4  g.)  was  dissolved  in 
ether  (8  g.)  and  alcohol  (16  g.),  saturated  with  hydrogen  chloride  at  10°, 
added.  A  red  coloration  was  produced  after  the  addition  of  the  alcohol. 
It  took  fully  2  days  for  the  reaction  to  go  to  completion.  A  beautiful 
pink  compound  was  obtained.  This  compound,  the  hydrochloride  of 
£-nitroso-w-bromo-monomethyl-aniline,  is  very  stable,  much  more  so 
than  the  hydrochloride  of  the  dimethyl-aniline  derivative.  It  was  kept 
3  weeks  in  an  open  dish  without  changing  color.  Its  melting-point  was 
not  sharp.  At  140°  it  turned  yellow,  and  at  168°  melted  with  apparent 
decomposition.  It  hydrolyzed  immediately  to  give  the  free  base  on  sus- 
pension in  water.  The  free  base  was  isolated  and  purified  by  the  same 
method  as  that  given  for  ^-nitroso-w-bromo-dimethyl-aniline. 

Subs.,  0.1055:  12. 1 1  cc.  dry  NZ  at  20  and  736  mm. 

Calc.  for  C7H7ON2Br:  N,  13.06.     Found:  12.95. 

The  free  base  is  green.  It  has  no  definite  melting-point.  It  turns  dark 
at  100°  and  explodes  at  124°.  An  ether  solution  of  the  base  is  yellowish- 
green  in  thin  layers  and  green  in  thick. 

p  -  Nitroso  -  phenol  -  o  -  mercuric  -  chloride,  HOC6H3(4)NO(2)HgCl.— 
Three  g.  of  0-phenol-mercuric  chloride  was  gradually  added  to  a  solution 
of  0.42  g.  of  sodium  hydroxide  and  0.86  g.  of  sodium  nitrite  in  23  cc.  of 
water.  The  solution  was  warmed  to  30-40°  and  a  few  drops  of  2  molar 
sodium  hydroxide  solution  added  to  it  until  all  of  the  o-phenol-mercuric- 
chloride  had  gone  into  solution.  When  finely  powdered,  it  goes  into  solu- 
tion rapidly  in  the  given  amount  of  sodium  hydroxide.2  It  was  cooled  to 
— 4°  or  — 5°  and  2  .3  g.  of  cone,  sulfuric  acid  in  6  cc.  of  water  added  very 
slowly.  The  flask  was  constantly  shaken  during  the  operation.  The 
addition  of  the  acid  should  take  about  45  minutes.  The  solution  first 
turned  pink,  due  to  the  formation  of  the  sodium  salt  of  the  ^-nitroso- 
phenol-<?-mercuric  chloride,  but  it  grew  darker  and  darker  in  color  as 
more  of  the  acid  was  added.  A  dark-colored  precipitate  was  also  formed. 
After  all  the  acid  had  been  added,  the  solution  was  shaken  for  1 5  minutes 
longer,  and  allowed  to  stand  in  a  freezing  mixture  for  2  hours  to  complete 
the  precipitation.  The  solution  was  then  filtered  and  the  residue,  after 
being  washed  a  few  times  with  small  amounts  of  cold  water,  dried  in  a 
vacuum  desiccator  over  solid  sodium  hydroxide  and  soda  lime.  A  beauti- 
ful bordeaux-colored  compound  was  thus  obtained  which  can  be  kept 
indefinitely  over  soda  lime  without  decomposition.  It  can  be  recrystallized 

1  Fisher  and  Hepp,  Ber.,  19,  2991  (1886). 

2  It  has  also  been  found  very  advantageous  to  moisten  the  o-phenol-mercuric- 
chloride  with  a  few  drops  of  alcohol.     It  then  dissolves  in  the  alkali  very  readily — for 
very  obvious  reasons. 


14 

from  xylene  in  which  it  is  slightly  soluble  and  also  from  anisol  from  which 
it  separates  in  very  small  needles  of  a  light  brown  color. 

Subs.,  0.1930:  6.72  cc.  dry  N2  at  22°  and  732.3  mm. 

Subs.,  0.1352:  AgCl,  0.0547. 

Calc.  for  C6H4O2NClHg:  N,  3.92;  Cl,  9.92.     Found:  N,  3.90;  Cl,  10.07. 

The  compound,  like  £>-nitroso-phenol,  gives  the  Lieberman's  nitros- 
amine  test.  It  is  partly  soluble  in  ether,  imparting  to  the  latter  an  in- 
tensely green  color.  It  behaves  in  all  respects  except  solubility,  like 
^-nitroso-phenol,  of  which  it  is  a  substituted  derivative  as  noticed  from 
the  method  of  preparation.  The  mercury  in  ortho  position  to  the  hy- 
droxyl  group  in  phenol  is  known  not  to  decrease  the  activity  of  the  para 
hydrogen  atom,  as  illustrated  by  the  fact  that  it  is  possible  to  couple 
ophenol-mercuric-chloride  with  diazo  compounds.1 

£-Nitroso-amline-0-mer  curie-chloride ,  NH2C6H3(4)NO(2)  HgCl .  — To 
2  g.  of  ^-nitroso-phenol-o-mercuric-chloride,  2 . 4  g.  of  ammonium  chloride, 
6 . 6  g.  of  dry  ammonium  acetate,  and  o .  2  g.  of  ammonium  carbonate  were 
added  and  the  mixture  warmed  on  the  water-bath  for  L/2  hour  with  vigor- 
ous stirring.2  It  was  then  poured  into  75  cc.  of  cold  water,  and  allowed  to 
stand  */2  hour.  A  slightly  brown  amorphous  precipitate  was  obtained. 
It  was  filtered  off,  washed  well  with  cold  water  until  the  washings  gave 
no  test  for  ammonia  to  Nessler's  reagent  and  dried 'in  a  vacuum  desic- 
cator over  sodium  hydroxide.  For  purification,  it  was  recrystallized  from 
anisol. 

Subs.,  0.1431,  0.1311:  (i)  9.80  cc.  dry  N2  at  23°  and  729.5  mm.,  (2)  8.90  cc.  dry 
No  at  19°  and  739.5  mm. 

Subs.,  0.1248:  AgCl,  0.0530. 

Subs.,  0.1252:  HgS,  0.0823. 

Calc.   for   C6HsON2ClHg:  N,    7-89;    Cl,   9.98;   Hg,   56.31.     Found:  N,   7-53J   Cl, 
10.18;  Hg,  56.57. 

The  compound  is  slightly  soluble  in  benzene  and  ether,  coloring  both 
green.  An  alcohol  solution  is  reddish-yellow. 

In  the  preparation  of  the  above  compound,  smaller  or  larger  quantities 
of  the  />-nitroso-phenol-0-mercuric-chloride  sometimes  remain  unchanged. 
vSo  it  is  always  advisable  to  test  the  ^-nitroso-aniline-o-mercuric-chloride 
by  the  Lieberman's  nitrosoamine  reaction  for  its  presence.  If  the  test  is 
positive,  the  precipitate  must  be  washed  by  decantation  with  a  2  molar 
solution  of  sodium  hydroxide  until  the  washings  are  colorless — the  phenol 
derivative  being  soluble.  It  is  then  washed  free  from  alkali  with  cold  water 
and  dried  in  a  vacuum  desiccator  over  sodium  hydroxide. 

Diphenylamino  -  tetramercuric  -  chloride,  HN/ — <f     y> — HgCl \  . — Di- 

V        I  /2 

HgCl 

1  Dimroth,  Centr.,  1901,  I,  450. 

2  Fisher  and  Hepp,  Ber.,  20,  2475  (1887). 


15 

phenylamine  (6 . 5  g.)  was  heated  with  mercuric  chloride  (2 . 7  g.)  until  the 
latter  seemed  to  go  into  solution.  A  crackling  noise  was  heard  and  the  reac- 
tion went  on  of  its  own  accord  with  the  evolution  of  heat.  The  solution 
was  first  yellow,  then  brown,  and  finally  dark  brown.  It  was  then  poured 
into  glacial  acetic  acid  and  boiled.  The  acid  was  decanted.  The  washing 
with  glacial  acetic  acid  was  continued  until  the  decanted  liquid  poured 
into  water  gave  no  precipitate,  indicating  that  the  product  was  free  from 
diphenylamine.  The  filtrate  was  tested  for  mercuric  chloride  until  the 
precipitate  was  washed  free  from  it.  A  light  yellow  amorphous  compound 
\vas  thus  obtained  as  a  residue  which,  after  being  boiled  with  alcohol, 
was  dried  in  a  vacuum  desiccator. 

Subs.,  0.8889:  10.20  cc.  of  No  at  21°  and  734.2  mm. 
Subs.,  0.1940:  AgCl,  0.1012. 
Subs.,  0.1699:  HgS,  0.1426. 

Calc.   for  daHrNC^Hgi:  N,    1.26;   Cl,    12.81;  Hg,   72.26.     Found:  N,    1.28;   Cl, 
12.98;  Hg,  72.10. 

The  compound  is  insoluble  in  all  organic  solvents.  It  does  not  melt 
when  heated  to  260°.  When  boiled  with  pyridine,  it  seems  to  undergo 
decomposition.  This  is  probably  a  ring  formation  as  large  quantities  of 
mercuric  chloride  are  found  in  the  pyridine.  It  is  being  investigated. 
From  consideration  of  analogous  cases  the  positions  taken  by  the  mer- 
cury are  most  likely  para  and  ortho  to  the  nitrogen.  Thus,  ^-toluidine 
yields  a  mono-substitued  derivative  when  treated  with  mercuric  acetate 
or  chloride,  o-toluidine  a  di-substituted  derivative,  and  w-toluidine  a 
tri-substituted  derivative.  In  these  compounds  mercury  occupies  the 
positions,  relative  to  the  nitrogen,  p,  p-o,  p-o-o,  respectively.  Further- 
more, the  literature  is  abundant  with  instances  of  similar  substitutions. 
In  no  case,  however,  has  a  mercury  compound  been  prepared  in  which 
mercury  would  occupy  a  position  meta  to  an  amino  nitrogen.  We  feel, 
therefore,  in  some  way  justified  in  assigning  the  above  structure  to  the 
diphenylamine  derivative. 

3,3  '-Mercuri-mercazine, 

H  H 

I N 1  ,  /,      /N 


-Hg- 

To  5  g.  of  diphenylamine-tetramercuric-chloride  in  60  cc.  of  alcohol  was 
added  10  g.  of  sodium  thiosulfate  in  a  little  water.  The  precipitate 
turned  dark  immediately.  The  solution  was  warmed  to  70°  and  kept 
at  that  temperature  for  15  minutes,  the  whole  being  shaken  during  the 
operation.  Sufficient  water  was  then  added  to  get  a  homogeneous  solu- 
tion, the  solution  boiled  a  few  minutes  and  then  filtered.  The  precipi- 


16 

tate  was  washed  with  alcohol  and  then  with  ether,  dried  and  then  ana- 
lyzed. 

Subs.,  0.1949:  4.60  cc.  of  dry  N2  at  21°  and  730.2  mm. 

Subs.,  0.1478:  HgS,  0.1142. 

Subs.,  0.3082:  CO2,  0.2739;  H2O,  2.09. 

Subs.,  0.2133:  AgCl,  0.0008. 

Calc.  for  Ci2HnONHg2:  N,  2.33;  C,  23.97;  H,  1.83;  Hg,  66.50.  Found:  N,  2.53; 
C,  24.22;  H,  2.09;  Hg,  66.60. 

The  compound  is  of  a  gray  color,  resembling  finely  precipitated  metallic 
mercury.  It  is  insoluble  in  all  organic  solvents.  When  heated  to  100° 
in  a  vacuum,  mercury  distils  over.  The  substance  is  unstable  when  treated 
with  nitric  acid.  The  product  of  nitration  is  soluble  in  sodium  hydroxide 
with  a  red  coloration. 

The  structural  formula  of  this  compound  is  of  great  interest.  The 
structure  which  suggests  itself  from  the  method  of  preparation  is, 

H 
N , 


1 Hg 1 

since  from  the  work  of  Pesci1  on  aniline  mercuri-acetate  and  similar 
compounds  it  is  quite  evident  that  the  sodium  thiosulfate  acts  in  the 
following  way 


\  ^° 

NHgOCf 


NCH, 

Boil  with  H20 


2NaC2H302 


The  intermediate  compounds  have  been  isolated  by  Pesci.  On  the  other 
hand,  the  para  mercury  bridge  would  give  rise  to  a  lo-atom  ring  with 
respect  to  the  nitrogen  which  would  probably  be  extraordinarily  unstable 
and,  therefore,  not  likely  to  form.  Then  again,  there  is  the  possibility 
of  the  formation  of  a  complex  molecule  of  the  type 

H 


Pesci,  Gazz.  chim.  ital.,  29,  I,  394  (1899). 


17 


We  have  not  been  able  so  far,  however-,  to  confirm  either  assumption, 
owing  to  the  insolubility  of  the  compound  in  all  solvents. 
'-3-Mercuric-chloride-di-nitro  (??)  diphenylamine , 

H  /\      NO2 

N- 


02N 


HgCl 


To  5  g.  of  diphenylamine-tetramercuric-chloride  20  g.  of  a  mixture  of 
cone,  nitric  acid  (2  parts  sp.  gr.  1.4),  sulfuric  acid  (i  part),  and  water 
(one  part)  were  added.  It  was  warmed  carefully  for  2  minutes.  The 
nitration  took  place  with  vigor.  When  the  reaction  had  completed  itself, 
the  contents  were  poured  into  water,  boiled,  and  the  solution  filtered. 
The  residue  was  washed  with  alcohol  and  ether  and  dried  in  a  vacuum 
desiccator. 

Subs.,  0.2491,  0.1732:  (i)  10.00  cc.  of  dry  N2  at  20°  and  728  mm.;  (2)  6.60  cc.  of 
dry  N2  at  2 1  °  and  740  mm. 

Subs.,  0.2518:  CO2,  0.1532;  H2O,  0.0159. 

Subs.,  0.2000:  AgCl,  0.0900. 

Subs.,  0.1320,  0.1831:  (i)  HgS,  0.0954;  (2)  0.1328. 

Calc.  for  CioHeC^NsClaHgs:  N,  4.39;  C,  14.93;  H,  0.63;  Cl,  11.03;  Hg,  62.24. 
Found:  N,  4.29;  C,  14.72;  H,  0.70;  Cl,  11.13;  Hg,  62.52. 

The  compound  is  of  a  light  brown  color.  It  is  insoluble  in  all  organic 
solvents.  It  is  partly  soluble  in  sodium  hydroxide1,  giving  the  solution 
a  red  coloration. 

Mercury-bis-3-di-nitro(?)-mercazine, 

H  xv      /N02     NO2\xv  H 

A  ' 


02N 


—  Hg 


2H,0. 


Starting .  with  the  above  nitro  compound,  this  compound  was  prepared 
by  the  same  method  as  used  for  3,3'-mercuri-mercazine. 

Subs.,  0.2248:  14.20  cc.  of  dry  N2  at  20°  and  738.7  mm. 
Subs. ,  0.1384:  CO2,  0.1218;  H. 
Subs.,  o.noi :  HgS,  0.0642. 

Calc.  for  C24HioOioN6Hg3:  N,   7.09;  C,   24.24;  H,    1.52;  Hg,  50.54.     Found:  N, 
7.16;  C,  24.01;  H,  1.98;  Hg,  50.26. 

The  compound  is  of  a  light  brown  color.  It  is  insoluble  in  all  organic 
solvents.  When  treated  with  sodium  hydroxide,  it  gives  to  the  latter 
a  light  red  coloration.  It  resembles  the  other  mercazine  derivative  in 
many  respects.  When  heated  in  a  vacuum  to  100°,  it  loses  mercury. 
Heated  to  54°  in  a  vacuum  for  fifteen  minutes,  it  loses  5.22%  of  water. 


18 

Conclusions. 

1.  A  few  methods  have  been  outlined  for  the   preparation    of    a    6- 
atom  heterocyclic  ring  containing  mercury  in  place  of  a  non-metal. 

2.  The  preparations  of  a  number  of  new  derivatives  of  m-bromo-dimethyl- 
aniline,  m-bromo-monomethyl -aniline  Bindshedler's  green,  mercury    de- 
rivatives   of    nitroso-phenol,    nitroso-aniline,    phenylamine    and    nitro- 
diphenylamine  have  been  described.     These  compounds  were  obtained 
as  a  result  of  carrying  out  the  above  procedures. 

In  conclusion,  the  writer  takes-  pleasure  in  acknowledging  gratefully  his 
appreciation  of  Dr.  Piccard's  guidance,  encouragement  and  personal  kind- 
ness in  the  course  of  this  work. 


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